EP0635360A1 - Film emboutissable, procédé pour sa fabrication et son utilisation - Google Patents

Film emboutissable, procédé pour sa fabrication et son utilisation Download PDF

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Publication number
EP0635360A1
EP0635360A1 EP94110650A EP94110650A EP0635360A1 EP 0635360 A1 EP0635360 A1 EP 0635360A1 EP 94110650 A EP94110650 A EP 94110650A EP 94110650 A EP94110650 A EP 94110650A EP 0635360 A1 EP0635360 A1 EP 0635360A1
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EP
European Patent Office
Prior art keywords
film
weight
shore
copolymer
propylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP94110650A
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German (de)
English (en)
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EP0635360B1 (fr
Inventor
Eberhardt Dous
Thambirajah Mathavan
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Benecke Kaliko AG
Original Assignee
Alkor GmbH Kunstoffverkauf
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Publication of EP0635360A1 publication Critical patent/EP0635360A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/16—EPM, i.e. ethylene-propylene copolymers; EPDM, i.e. ethylene-propylene-diene copolymers; EPT, i.e. ethylene-propylene terpolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
    • B29L2031/3005—Body finishings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/408—Matt, dull surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/72—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof

Definitions

  • the present invention relates to a deep-drawable composite film which contains a polyolefin-containing top film and at least one polyolefin-containing bottom film which differs qualitatively and / or quantitatively from the composition of the top film, and optionally a surface protective layer, the top film containing certain quantities of weight a) a crosslinked PP-EPDM and b) one uncrosslinked propylene block copolymer or heterophasic propylene block polymer, where b) is partially replaced by a polymer containing reactive groups and / or ionomer c).
  • the bottom film contains at least two different polyolefins or polyolefin-containing polymers, e.g. partially crosslinked EPDM, polypropylene and / or reactive group-containing polymers and / or ionomers and / or polymeric crosslinking agents or one or more of the aforementioned polyolefin-containing polymers and ethylene-vinyl acetate copolymer.
  • polyolefins or polyolefin-containing polymers e.g. partially crosslinked EPDM, polypropylene and / or reactive group-containing polymers and / or ionomers and / or polymeric crosslinking agents or one or more of the aforementioned polyolefin-containing polymers and ethylene-vinyl acetate copolymer.
  • the aim and object of the present invention was to achieve an improved film with improved properties or processing properties compared to the prior art.
  • the film should have good or improved grain stability, the surfaces should be matt without an additional matting agent or have a certain mattness or degree of matting.
  • the film should have good thermoformability and should also be able to be processed into molded parts or articles to which relatively high demands are made.
  • Such fields of application are, for example, molded parts, objects or deep-drawn parts for motor vehicles, in particular motor vehicle interior trim.
  • thermoformable composite film which contains a polyolefin-containing top film and at least one polyolefin-containing bottom film which differs qualitatively and / or quantitatively from the composition of the top film, and optionally a surface protective layer.
  • the lower film or lower films contain (or contain) at least two different polyolefins or polyolefin- or olefin-containing polymers, -co-, -ter-, -graft- or -block polymers.
  • the composite film according to the invention is a flexible thermoformable motor vehicle film or web, which is particularly well suited for the production of thermoformed molded parts with a uniform matt surface for motor vehicle films for interior trim.
  • the mattness of this film is largely independent of the deformation temperature and the degree of deformation, i.e. The same or approximately the same mattness of the film surface or of the thermoformed molded part produced therefrom is given at all points of the molded part.
  • the top film preferably contains a dynamically cross-linked or partially cross-linked PP-EPDM or PP-EPDM mixtures or alloys.
  • the components a), b) and c) of the top film are optionally used in combination with processing aids, additives, fillers, dyes and / or color pigments.
  • the polypropylene block of the uncrosslinked heterophase polypropylene block polymer preferably consists of a propylene, co and / or block polymer.
  • the elastomer content of the heterophasic polypropylene block copolymer is 40 to 70% by weight (based on 100 parts by weight of the uncrosslinked heterophasic propylene block copolymer).
  • the proportion of elastomer in the heterophasic polypropylene block copolymer is 35.5 to 48% by weight, preferably 36 to 45% by weight (based on 100 parts by weight of the uncrosslinked heterophasic propylene block polymer).
  • the elastomer of the ethylene-propylene copolymer has an ethylene content of 20 to 70% by weight, preferably 30 to 60% by weight, and a propylene content of 80 to 30% by weight, preferably 70 to 40 Wt .-%, and has a molecular weight greater than 100,000, preferably greater than 150,000.
  • a dynamically cross-linked PP-EPDM blend in the top and / or bottom film with a particle size of the cross-linked elastomer phase of 0.5 to 15 ⁇ m improves the deformation range, the uniformity of thermal expansion and the grain pattern.
  • An improved grain pattern means that the disproportionate elongation of the grain valleys is limited by the strength increasing with increasing elongation (strain hardening). In order to achieve this effect, homogeneous incorporation of the cross-linked PP-EPDM blends and a particulate elastomer structure are necessary.
  • the degree of cross-linking in complex systems indirectly defined by the compression set at 70 ° C after 22 hours (DIN 53517), should be between 25 and 60.
  • a block polymer with an Mfi 230 / 2.16 g / 10 min of 0.3 to 8, preferably 0.5 to 7, is preferably used as the heterophasic propylene block polymer.
  • PP-EPDM preferably dynamically cross-linked or partially cross-linked PP-EPDM, those with a density between 0.83 to 0.96 g / cm 3, preferably 0.87 to 0, are preferably used for the top and / or bottom film (s).
  • the PP-EPDM which is selected for this purpose, preferably has a bending module (initial flexural modulus) - measured according to ASTM D 790 with a 2 mm thick film web - from 80 to 400 MPa, preferably 100 to 300 MPa.
  • thermoformable composite films according to the invention have a gloss level according to DIN 57530/60 ° of 0.5 to 5 on the top film, which is neither significantly influenced by the required deformation temperature nor by the thermoforming ratio. This feature thus distinguishes the films according to the invention from the knowledge gained from previous experience with films which have been matted by fillers or embossing.
  • thermoforming of the composite film according to the invention can be carried out in a wide temperature range of approximately 140 to 200 ° C., preferably 150 to 185 ° C., without any particular difficulties.
  • the film is extremely deep-drawable and can be used both in the positive deep-drawing process and in the negative deep-drawing process.
  • Using the composition it is possible to obtain deep-drawn films with a Shore D hardness of 25 to 60, preferably 30 to 55 and a Gardner gloss degree of 60 ° C. of 0.5 to 1.5, measured on the deep-drawn molded part.
  • the motor vehicle composite film webs for the interior trim also have the advantage of high aging stability against light and heat and low fog values.
  • the top and / or bottom film has a filler content of 0 to 30 parts by weight, 0 to 20 parts by weight (based on 100 parts by weight of plastic).
  • the known fillers preferably talc and / or SiO2 with an average particle size of 0.01 to 20 ⁇ m, preferably 0.05 to 10 ⁇ m, can be used as fillers.
  • processing aids i.a. preferably heat and / or light stabilizers used for polyolefins.
  • processing aids or additives include Lubricants or mixtures of lubricants are used.
  • an adhesion promoter layer is preferably arranged below the film layer.
  • the adhesion promoter layer preferably consists of or contains acrylates, polyurethane or acrylate-polyurethane mixtures.
  • a foam layer, a carrier layer, a fabric layer and / or support layer is preferably arranged below the film layer or adhesion promoter layer.
  • the foam layer preferably contains or consists of a polyolefin foam, or a polyurethane foam.
  • the top film preferably has an average thickness of 60 to 500 ⁇ m, preferably 100 to 350 ⁇ m.
  • the lower film or lower films have an average thickness of 100 to 2000 ⁇ m, preferably 500 to 1500 ⁇ m, the lower film or lower films having an overall thickness which is more than 1.5 times, preferably 2 or more times the upper film.
  • the composite film according to the invention is very thermoformable and is used to produce low-stress molded parts with precise reproduction or reproduction of surface structures that are stable in shape or temperature.
  • the composite film is preferably processed or processed in the positive deep-drawing process and / or negative deep-drawing process.
  • the composite material preferably has a foam layer, e.g. Polyurethane foam, but preferably polyolefin foam on and / or is provided with a carrier layer or a carrier and / or a support layer and / or a grid or fabric layer.
  • the film or layer is provided with decorations, grains, embossings and the like. It is grain-resistant, easy to grip and can be printed. Using the composite film according to the invention, it is possible to produce molded parts or articles whose surface has good grain stability even when stored under heat.
  • the bottom film contains at least one partially cross-linked EPDM and a propylene homo-, copolymer or graft polymer with or without reactive groups, a PP-EPDM or dynamically cross-linked or partially cross-linked PP-EPDM with at least one of the components b or c of the top film and / or at least one polymer containing reactive groups and / or ionomer or consists thereof.
  • the lower film (based on the plastic content) consists of 65 to 90% by weight (based on 100% by weight plastic of the lower film) made of propylene homo-, -co-, -ter- and / or -block polymer and 35 to 10% by weight of ethylene-vinyl acetate copolymer with a vinyl acetate content of 10 to 40% by weight, preferably 20 to 35% by weight, a plastic or the mixture being treated with 0.1 to 5% by weight, preferably 0.2 to 1.5% by weight, of at least one peroxide or a compound containing peroxide groups.
  • the lower film preferably consists of 70 to 85% by weight, preferably 75 to 83% by weight (based on 100% by weight plastic of the lower film) of propylene homopolymer, co polymer, ter polymer and / or block polymer and 20 to 15% by weight, preferably 25 to 17% by weight, of ethylene-vinyl acetate copolymer.
  • the lower film contains at least one partially crosslinked EPDM, a propylene homo-, copolymer or graft polymer with or without reactive groups and additionally another block, di-block containing olefin or polyolefin and / or styrene or polystyrene.
  • the constituents of the lower film are preferably selected such that the lower film produced therefrom (based on the initial or initial cross section of the lower film has a maximum tensile stress in the range from 20x103 to 70x103 Pa and / or that the tensile stress curve at an elongation above 150 %, preferably over 300% elongation, runs approximately parallel to the elongation axis after reaching the maximum.
  • the objects, moldings, parts and the like produced or deep-drawn therefrom which preferably contain a foam layer, carrier layer or a carrier, support layer and / or a grid or fabric layer, are preferably used for control panels or dashboards for motor vehicles, side wall parts for motor vehicles, door panels for Motor vehicles, roof linings (headlining), interior rear wall parts for motor vehicles (parcel shelf) and other interior trim parts or objects for motor vehicles are used.
  • the carrier layer and / or foam layer contains polyolefins or is based on polyolefins.
  • the polymers and / or ionomers of the lower film containing reactive groups preferably contain alkali and / or alkaline earth metal ions and / or zinc ions as metal ions.
  • the reactive group-containing polymers and / or ionomers contain alkyl acrylates and / or alkyl methacrylates with 1 to 8 carbon atoms.
  • the propylene or polypropylene content (content of propylene homo-, -co-, -ter- or -blockpolymerisat) of the cross-linked PP-EPDM (component a) of the top film based on 100 parts by weight of that in the top film contained PP-EPDM between 60 to 90 wt .-%, preferably 65 to 85 wt .-%, while the EPDM, which has been crosslinked with a peroxide or a compound containing peroxide groups, a weight fraction of 40 to 10 wt .-%, preferably 35 to 15% by weight.
  • the upper film has a Shore D hardness or is adjusted to it, which is more than 3 Shore D units, preferably 5 to 10 Shore D units, lower than the Shore D hardness of the lower film ( n) and / or that the surface tension of the top film is set to a value of greater than 40 mN / m.
  • the top film is made using at least one plastic with a lower Shore D hardness and at least one component or plastic with a higher Shore D hardness to a Shore D hardness of less than 37, preferably to a Shore D hardness of 28 to 35 set and the Shore D hardness of the lower film (s) is at least 38 Shore D, preferably 39 to 48 Shore D.
  • At least one layer containing polyacrylate, polymethacrylate and / or polyurethane is arranged above the top film or on the film surface and / or below the bottom film, the layer thickness of which is less than the layer thickness of the top film or bottom film, the layer thickness preferably being Coating is less than 50% of the layer thickness of the top or bottom film (s).
  • the upper film and, if appropriate, partial areas of the lower film (s) are preferably embossed or grained and provided with at least one layer or coating containing polyacrylate, polymethacrylate and / or polyurethane which contains 0.01 to 18% by weight, preferably 0.1 to Contains 12 wt .-%, at least one finely divided matting agent and is coated by application of diluent.
  • the polyacrylate-, polymethacrylate- and / or polyurethane-containing layer (s) or layer (s) (based on the plastic portion) or layer (s) or coating (s) arranged below the bottom film (s) preferably contain at least one antistatic agent and / or at least one adhesion-promoting chemical agent, preferably very finely divided carbon or carbon black with an average particle size below 100 nm, preferably between 10 to 80 nm, and / or at least one very finely divided silica or a very finely divided silicon dioxide and / or very finely divided silicate with an average grain diameter below 4 ⁇ m, preferably less than 3 ⁇ m.
  • the lower film or lower films (based on 100 parts by weight of plastic of the lower film or lower films) consists of 1 to 60% by weight, preferably 5 to 55% by weight, at least one partially networked EPDM 12 to 30% by weight, preferably 13 to 25% by weight, Propylene homo-, copolymer or graft polymer with or without reactive groups 77 to 9.5% by weight, preferably 73 to 19.0% by weight, at least one reactive group-containing polymer and / or ionomer based on ethylene and methacrylic acid or acrylic acid, the acid groups partially containing metal ions or being neutralized by metal ions and 10 to 0.5% by weight, preferably 9 to 1.0% by weight, at least one polymeric crosslinking agent containing reactive groups which comprises more than 51% by weight (based on 100 parts by weight of the polymeric crosslinking agent) of ethylene or other olefin groups and 1 to 49% by weight of acrylate and / or methacrylate groups and reactive Contains groups, the reactive groups
  • the polymeric crosslinking agent of the lower film or lower films containing reactive groups has in addition to acrylate and / or methacrylate groups or acrylic acid and / or methacrylic acid groups and more than 51% by weight of ethylene and / or olefin or (CH2) or CH groups, epoxy groups or epoxy-like groups, preferably Glycidyl groups.
  • the reactive groups-containing polymers and / or ionomers of the lower film preferably contain alkali and / or alkaline earth metal ions and / or zinc ions as metal ions.
  • the reactive group-containing polymers and / or ionomers contain alkyl acrylates and / or alkyl methacrylates with 1 to 8 carbon atoms.
  • the plastic film or plastic film web contains or consists of at least one lower film, which as a plastic component or plastic mixture (x) contains 5 to 80 parts by weight, preferably 10 to 60 parts by weight, of at least one polymer containing elastic reactive groups or at least one thermoplastic reactive group-containing elastomer or a reactive group-containing polymer or polymer mixture with a proportion of elastic polymers of more than 60% by weight, preferably more than 75% by weight (based on 100 parts by weight of the elastomer-containing polymer or polymer mixture), (y) 95 to 20 parts by weight, preferably 90 to 40 parts by weight, of at least one reactive group-containing polyolefin or polyolefin-containing ionomer, preferably at least one reactive group-containing olefin co-, -ter- and / or - graft polymer and / or an ionomer containing or based on a polyolefin homo-, -co-, -ter- and
  • the reactive groups of the reactive group-containing polyolefin and / or of the additional reactive group-containing elastic polymer or thermoplastic elastomer are preferably carboxyl, hydroxyl, anhydride, amine, amide, isocyanate, epoxy and / or Nitrile groups.
  • the proportion by weight of reactive groups is 0.2 to 30% by weight, preferably 0.3 to 25% by weight, based on the elastic polymer (s) containing reactive groups (calculated with 100 parts by weight) or containing reactive groups thermoplastic elastomers or polymer mixtures according to (x) and 0.2 to 25% by weight, preferably 0.5 to 20% by weight, based on the polyolefin (s) or polyolefin-containing polyolefin (s) containing the reactive groups Ionomers (n) according to (y).
  • the elastic polymer and / or thermoplastic elastomer containing reactive groups consists of mixtures of different reactive and non-reactive polymers, but the total content of reactive groups in the mixtures is 0.2 to 30% by weight, preferably 0.3 to 25% by weight .-% (based on 100 wt .-% of the reactive polymer-containing polymer mixture).
  • the plastic film in particular during production, contains the plastic mixture consisting of (x) and (Z) per 100 parts by weight (z) 0.5 to 30 parts by weight, preferably 5 to 25 parts by weight , another thermoplastic (but excluding a free, reactive group-containing polyolefin or polyolefinic ionomer or thermoplastic elastomer or elastic polymer).
  • At least the lower film contains 100 parts by weight of (x) and (y) or of (x), (y) and (z) additionally 0.01 to 6 parts by weight of at least one processing aid or Additive, preferably at least one stabilizer, antioxidant, UV absorber, lubricant and / or antistatic in one layer or the plastic film or the plastic film web consists of it.
  • the plastic molding compound or plastic-containing molding compound for producing the lower film or film sheet or at least one layer of the lower film or lower film web contains 5 to 80 parts by weight, preferably 10 to 60 parts by weight, of at least one elastic reactive group containing polymers and / or at least one thermoplastic reactive group-containing elastomer or a reactive group-containing polymer or polymer mixture with a proportion of elastic polymers of more than 60% by weight, preferably more than 75% by weight (based on 100% by weight Parts of the elastomer-containing polymer or polymer mixture), (y) 95 to 20 parts by weight, preferably 90 to 40 parts by weight, of at least one reactive group-containing polyolefin or polyolefin-containing ionomer, preferably at least one reactive group-containing olefin co-, -ter- and / or graft polymer and / or an ionomer containing or on the Ba sis a polyolefin copolymer, terpolymer
  • the reactive group-containing polyolefin (y) consists of a mixture or alloy and / or a co- or graft polymer of an olefin, preferably ethylene and / or propylene, and a carboxylic acid and / or its anhydride containing at least one unsaturated bond , preferably acrylic acid, methacrylic acid, maleic acid and / or maleic anhydride, and / or an olefin or polyolefin, preferably ethylene or polyethylene and a compound containing at least one epoxy group, preferably methacrylate glycide or a copolymer of one or more of these compounds or containing them.
  • the elastic polymer (s) which have reactive groups or compounds containing additional reactive groups consists of a reactive group-containing ethylene-propylene copolymer (EPM), a reactive group-containing polymer or reactively modified ethylene-propylene-diene copolymer (EPDM), reactive group-containing diblock polymers of styrene with butadiene, with isoprene, with ethylene-butylene or with ethylene-propylene, preferably from reactive group-containing styrene-3-block polymers with ethylene-butylene and Ethylene propylene, an elastic polyester and / or polyether ester, polyester amide, polyether amide or copolyester or polyurethane or polyether urethane segment polymers.
  • EPM reactive group-containing ethylene-propylene copolymer
  • EPDM reactively modified ethylene-propylene-diene copolymer
  • a peroxidic crosslinking agent or an organic or polymeric crosslinking agent containing reactive groups is also used in amounts by weight of 0.1 to 20 parts by weight, preferably 0.3 to 12 parts by weight.
  • the polymeric crosslinking agent of the bottom film or bottom films containing reactive groups has, in addition to acrylate and / or methacrylate groups or acrylic acid and / or methacrylic acid groups and more than 51% by weight of ethylene and / or olefin or ( CH2) - or CH groups epoxy groups or epoxy-like groups, preferably glycidyl groups.
  • the polymers and / or ionomers of the lower film containing reactive groups preferably contain alkali and / or alkaline earth metal ions and / or zinc ions as metal ions.
  • the reactive group-containing polymers and / or ionomers contain alkyl acrylates and / or alkyl methacrylates with 1 to 8 carbon atoms.
  • Part c can include represent a vinyl acetate homo, co or terpolymer or another polymer containing acid and / or ester groups (EA, EAA, EMA).
  • the present invention further relates to a method for producing the thermoformable composite film, wherein two or more extruders are used for the production of the plastic film, which are equipped with a slot extrusion die.
  • the components a) to c) of the top film and at least one further extruder the components of the bottom film or bottom films are extruded at from 150 to 280 ° C., preferably from 180 to 250 ° C., at least one extruder, with two or more Components of the lower film, using a twin-screw extruder, partially react or couple at the extrusion temperature and the composite film as a coextrusion film will be produced.
  • the Shore D hardness of the top film is achieved using and / or using at least one plastic containing polyolefin or polyolefin groups with a lower Shore D hardness (measured according to DIN 53505) and optionally using at least one containing polyolefin or polyolefin groups Plastic with a higher Shore D hardness is set to a Shore D value that is more than 3 Shore D units, preferably 5 to 10 Shore D units, lower than the Shore D value of the lower film arranged below.
  • the hardness of the top film is selected to a hardness of less than 37 D-Shore, preferably 28 to 35 D-Shore (measured according to DIN 53505), by selecting the polyolefin and / or olefin group-containing plastics or constituents with lower and higher Shore D hardness and their weight amounts ), and the hardness of the lower film (s) is set to at least 38 D-Shore, preferably 39 to 46 D-Shore.
  • the top film (on its surface facing away from the bottom film) and / or the bottom film (on its surface facing away from the top film) are containing at least one polyacrylate-, polymethacrylate- and / or polyurethane-containing and diluent, preferably organic-chemical solvent Coating using a coating agent application process, preferably using a spraying, spraying, brushing, roller or printing roll application process, the coating of the top film being 0.01 to 18% by weight, preferably 0.1 to 12% by weight. %, contains at least one finely divided matting agent.
  • At least one antistatic agent and / or at least one adhesion-promoting chemical agent, preferably more finely divided, is preferred for the layer or coating arranged below the lower film Carbon or carbon black with an average particle size below 100 nm, preferably between 10 and 80 nm, and / or at least one very finely divided silica or a very fine silicon dioxide and / or silicate with an average grain diameter below 4 ⁇ m, preferably below 3 ⁇ m.
  • the present invention further relates to the use of the composite film alone or in combination with a foam layer, carrier layer or a carrier, support layer, spacer layer or a mesh or fabric layer for the production of motor vehicle interior linings, preferably for control panels or dashboards for motor vehicles, side panels for motor vehicles, door linings for Motor vehicles, roof linings (car headlining), interior rear wall parts for motor vehicles (parcel shelf) and other interior lining parts or objects for motor vehicles.
  • FIGS. 1 and 2 some exemplary embodiments of the composite film according to the invention are shown schematically, the thickness dimensions not corresponding to the actual thicknesses of the layers (particularly in the case of the surface protective layer or lacquer layer, which in practice is preferably between 8 and 60 ⁇ m) 10 to 50 ⁇ m, is).
  • the paint or surface protection layer is shown under (1), which is preferably applied in the form of a compound or solvent such as synthetic resin for the surface coating.
  • the lower film (s) (3) is or are arranged under the upper film (2).
  • a further layer (4) is shown schematically in FIG.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
EP94110650A 1993-07-17 1994-07-08 Film emboutissable, procédé pour sa fabrication et son utilisation Expired - Lifetime EP0635360B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4324090 1993-07-17
DE4324090 1993-07-17
DE4330200 1993-09-07
DE4330200 1993-09-07

Publications (2)

Publication Number Publication Date
EP0635360A1 true EP0635360A1 (fr) 1995-01-25
EP0635360B1 EP0635360B1 (fr) 1999-12-01

Family

ID=25927789

Family Applications (1)

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EP94110650A Expired - Lifetime EP0635360B1 (fr) 1993-07-17 1994-07-08 Film emboutissable, procédé pour sa fabrication et son utilisation

Country Status (5)

Country Link
EP (1) EP0635360B1 (fr)
AT (1) ATE187122T1 (fr)
CZ (1) CZ172494A3 (fr)
DE (2) DE4423883A1 (fr)
ES (1) ES2140480T3 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0868995A2 (fr) * 1997-04-01 1998-10-07 Grand Polymer Co., Ltd. Procédé pour le moulage d'un composant de garniture extérieure pour un automobile, feuille ou couche laminée pour son utilisation et composant de garniture extérieure pour un automobile
US6436531B1 (en) 1998-07-20 2002-08-20 3M Innovative Properties Company Polymer blends and tapes therefrom
EP1238796A2 (fr) * 2001-03-10 2002-09-11 FOLIEPACK Kunststoffwerk GmbH Feuille multicouche emboutie
US7335424B2 (en) 2001-03-29 2008-02-26 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
US7405008B2 (en) 2001-03-29 2008-07-29 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
WO2021041618A1 (fr) * 2019-08-29 2021-03-04 Dow Global Technologies Llc Mélanges de polymères à propriétés thermiques améliorées

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1288487B1 (it) * 1996-08-05 1998-09-22 Gor Applic Speciali Srl Pannello termoformabile con rivestimento superficiale del tipo anologo alla finta pelle, o simili e procedimento per la fabbricazione
DE19835612C2 (de) * 1997-08-07 2003-07-03 Toyoda Gosei Kk Einstückig geformte Gegenstände
EP0928677A1 (fr) * 1997-12-29 1999-07-14 COMMER S.p.A. Procédé et installation pour la production d'éléments de garniture multicouches pour véhicules
DE19915314A1 (de) * 1999-04-03 2000-10-05 Alkor Gmbh Verbundwerkstoff und Verfahren zu dessen Herstellung
DE19923780A1 (de) * 1999-05-22 2000-11-23 Beiersdorf Ag Unverstreckte Oberflächenschutzfolie aus Polypropylenblockcopolymer
WO2001078981A1 (fr) 2000-04-14 2001-10-25 E.I. Dupont De Nemours And Company Surfaçage decoratif ionomerique co-extrude et multicouches
DE10046982C1 (de) * 2000-09-22 2001-12-13 Dornier Gmbh Fahrzeuginnenraumverkleidung mit verringerter Blendwirkung an der Windschutzscheibe oder Heckscheibe
EP2177354B1 (fr) 2008-05-05 2012-08-08 A. Schulman, Inc. Structure de support laminée
DE102009025994A1 (de) 2009-06-18 2010-12-23 Benecke-Kaliko Ag Verfahren zur Herstellung eines Formkörpers
DE102009025995A1 (de) 2009-06-18 2011-03-31 Benecke-Kaliko Ag Verfahren zur Herstellung eines Formkörpers

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0146349A2 (fr) * 1983-12-14 1985-06-26 Mitsui Petrochemical Industries, Ltd. Laminé, sa fabrication et son utilisation
EP0428851A1 (fr) * 1989-10-02 1991-05-29 Sarna Patent- Und Lizenz-Ag Lés d'étanchéité
EP0468947A2 (fr) * 1990-07-26 1992-01-29 Advanced Elastomer Systems, L.P. Mélanges dynamiquement vulcanisés à base d'un copolymère d'éthylène modifié
US5206294A (en) * 1991-11-06 1993-04-27 E. I. Du Pont De Nemours And Company Thermoplastic polymer alloy composition
EP0568815A1 (fr) * 1992-04-04 1993-11-10 J.H. Benecke AG Feuille ou objet formé à base d'une matière thermoplastique contenant un terpolymère

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0146349A2 (fr) * 1983-12-14 1985-06-26 Mitsui Petrochemical Industries, Ltd. Laminé, sa fabrication et son utilisation
EP0428851A1 (fr) * 1989-10-02 1991-05-29 Sarna Patent- Und Lizenz-Ag Lés d'étanchéité
EP0468947A2 (fr) * 1990-07-26 1992-01-29 Advanced Elastomer Systems, L.P. Mélanges dynamiquement vulcanisés à base d'un copolymère d'éthylène modifié
US5206294A (en) * 1991-11-06 1993-04-27 E. I. Du Pont De Nemours And Company Thermoplastic polymer alloy composition
EP0568815A1 (fr) * 1992-04-04 1993-11-10 J.H. Benecke AG Feuille ou objet formé à base d'une matière thermoplastique contenant un terpolymère

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0868995A2 (fr) * 1997-04-01 1998-10-07 Grand Polymer Co., Ltd. Procédé pour le moulage d'un composant de garniture extérieure pour un automobile, feuille ou couche laminée pour son utilisation et composant de garniture extérieure pour un automobile
EP0868995A3 (fr) * 1997-04-01 1999-04-28 Grand Polymer Co., Ltd. Procédé pour le moulage d'un composant de garniture extérieure pour une automobile, feuille ou couche laminée pour son utilisation et composant de garniture extérieure pour une automobile
US6436531B1 (en) 1998-07-20 2002-08-20 3M Innovative Properties Company Polymer blends and tapes therefrom
EP1238796A2 (fr) * 2001-03-10 2002-09-11 FOLIEPACK Kunststoffwerk GmbH Feuille multicouche emboutie
EP1238796A3 (fr) * 2001-03-10 2002-10-02 FOLIEPACK Kunststoffwerk GmbH Feuille multicouche emboutie
US7335424B2 (en) 2001-03-29 2008-02-26 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
US7405008B2 (en) 2001-03-29 2008-07-29 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
WO2021041618A1 (fr) * 2019-08-29 2021-03-04 Dow Global Technologies Llc Mélanges de polymères à propriétés thermiques améliorées
US11939457B2 (en) 2019-08-29 2024-03-26 Dow Global Technologies Llc Polymer blends having improved thermal properties

Also Published As

Publication number Publication date
ATE187122T1 (de) 1999-12-15
CZ172494A3 (en) 1995-02-15
DE4423883A1 (de) 1995-01-19
ES2140480T3 (es) 2000-03-01
DE59408960D1 (de) 2000-01-05
EP0635360B1 (fr) 1999-12-01

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